6-Bromo-4-hydrazinyl-idene-1-methyl-3H-2λ,1-benzothia-zine-2,2-dione.

In the title mol-ecule, C(9)H(10)BrN(3)O(2)S, the thia-zine ring has an envelope conformation with the S atom at the flap. The geometry around the S atom is distorted tetra-hedral. In the crystal, inversion dimers linked by pairs of N-H⋯N hydrogen bonds occur, generating R(2) (2)(6) ring motifs. N-H⋯O hydrogen bonds and C-H⋯O inter-actions connect the dimers, forming a three-dimentional network structure.

Related literature

For the related structures of 6-bromo-1-methyl-1H-2,1-benzo­thia­zin-4(3H)-one 2,2-dioxide and 6-bromo-1-ethyl-1H-2,1-benzo­thia­zin-4(3H)-one 2,2-dioxide, see: Shafiq et al. (2009a ▶,b ▶), respectively. For the structures of other benzothia­zine derivatives, see: Shafiq et al. (2011 ▶); Arshad et al. (2011 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C9H10BrN3O2S

M = 304.17

Monoclinic,

a = 10.1483 (5) Å

b = 9.6375 (4) Å

c = 11.2118 (5) Å

β = 92.278 (2)°

V = 1095.69 (9) Å3

Z = 4

Mo Kα radiation

μ = 3.93 mm−1

T = 296 K

0.21 × 0.09 × 0.07 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.492, T max = 0.771

12176 measured reflections

2719 independent reflections

1972 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.079

S = 1.01

2719 reflections

152 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811027930/su2288sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027930/su2288Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811027930/su2288Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C9H10BrN3O2S	F(000) = 608
Mr = 304.17	Dx = 1.844 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3531 reflections
a = 10.1483 (5) Å	θ = 2.7–24.7°
b = 9.6375 (4) Å	µ = 3.93 mm−1
c = 11.2118 (5) Å	T = 296 K
β = 92.278 (2)°	Needle, yellow
V = 1095.69 (9) Å3	0.21 × 0.09 × 0.07 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	2719 independent reflections
Radiation source: fine-focus sealed tube	1972 reflections with I > 2σ(I)
graphite	Rint = 0.037
φ and ω scans	θmax = 28.3°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→13
Tmin = 0.492, Tmax = 0.771	k = −12→7
12176 measured reflections	l = −14→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0403P)2 + 0.1092P] where P = (Fo2 + 2Fc2)/3
2719 reflections	(Δ/σ)max = 0.001
152 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Br1	0.94817 (3)	0.62148 (3)	1.15166 (3)	0.04753 (12)
S1	0.86913 (6)	1.05109 (6)	0.65175 (5)	0.03060 (16)
O1	0.81377 (18)	0.92236 (19)	0.60884 (16)	0.0413 (4)
O2	0.90132 (19)	1.15392 (19)	0.56664 (16)	0.0433 (5)
N1	1.00013 (19)	1.0224 (2)	0.73776 (18)	0.0321 (5)
N2	0.6567 (2)	1.0222 (2)	0.9307 (2)	0.0400 (5)
N3	0.5556 (3)	1.1148 (3)	0.9019 (3)	0.0551 (7)
H32	0.507 (4)	1.115 (3)	0.962 (3)	0.066*
H31	0.586 (3)	1.199 (4)	0.881 (3)	0.066*
C1	0.9838 (2)	0.9263 (2)	0.8314 (2)	0.0290 (5)
C2	1.0852 (3)	0.8338 (3)	0.8633 (2)	0.0363 (6)
H2	1.1616	0.8335	0.8202	0.044*
C3	1.0743 (3)	0.7436 (3)	0.9567 (2)	0.0377 (6)
H3	1.1427	0.6829	0.9774	0.045*
C4	0.9602 (3)	0.7443 (2)	1.0195 (2)	0.0341 (6)
C5	0.8576 (2)	0.8322 (2)	0.9895 (2)	0.0319 (6)
H5	0.7813	0.8299	1.0328	0.038*
C6	0.8669 (2)	0.9253 (2)	0.8943 (2)	0.0274 (5)
C7	0.7567 (2)	1.0212 (2)	0.8646 (2)	0.0290 (5)
C8	0.7637 (3)	1.1175 (2)	0.7582 (2)	0.0343 (6)
H8A	0.7954	1.2077	0.7848	0.041*
H8B	0.6761	1.1295	0.7219	0.041*
C9	1.1299 (3)	1.0488 (3)	0.6900 (3)	0.0457 (7)
H9A	1.1927	1.0658	0.7546	0.069*
H9B	1.1250	1.1284	0.6385	0.069*
H9C	1.1571	0.9694	0.6454	0.069*

	U11	U22	U33	U12	U13	U23
Br1	0.04682 (19)	0.04001 (17)	0.0552 (2)	−0.00435 (13)	−0.00552 (14)	0.01513 (13)
S1	0.0277 (3)	0.0349 (3)	0.0292 (3)	0.0003 (3)	0.0004 (3)	0.0005 (2)
O1	0.0432 (11)	0.0436 (10)	0.0366 (10)	−0.0068 (9)	−0.0041 (8)	−0.0078 (8)
O2	0.0411 (11)	0.0484 (11)	0.0406 (11)	0.0029 (9)	0.0046 (9)	0.0129 (8)
N1	0.0234 (11)	0.0400 (11)	0.0330 (12)	−0.0015 (9)	0.0008 (9)	0.0032 (9)
N2	0.0375 (13)	0.0384 (12)	0.0447 (14)	0.0089 (10)	0.0113 (11)	0.0073 (10)
N3	0.0439 (16)	0.0518 (16)	0.071 (2)	0.0180 (13)	0.0243 (14)	0.0177 (14)
C1	0.0265 (13)	0.0311 (12)	0.0290 (13)	−0.0005 (10)	−0.0034 (10)	−0.0058 (10)
C2	0.0283 (14)	0.0411 (14)	0.0394 (16)	0.0041 (11)	0.0000 (12)	−0.0047 (11)
C3	0.0337 (15)	0.0352 (13)	0.0436 (16)	0.0073 (11)	−0.0062 (12)	−0.0033 (11)
C4	0.0395 (15)	0.0257 (11)	0.0362 (14)	−0.0052 (10)	−0.0086 (12)	−0.0002 (10)
C5	0.0300 (14)	0.0319 (12)	0.0335 (14)	−0.0037 (10)	−0.0015 (11)	−0.0033 (10)
C6	0.0283 (13)	0.0259 (11)	0.0279 (13)	−0.0023 (10)	−0.0021 (10)	−0.0050 (9)
C7	0.0276 (13)	0.0293 (12)	0.0302 (13)	−0.0001 (10)	0.0022 (10)	−0.0035 (10)
C8	0.0322 (14)	0.0348 (13)	0.0360 (14)	0.0045 (11)	0.0028 (11)	0.0017 (11)
C9	0.0265 (14)	0.0676 (19)	0.0432 (16)	−0.0013 (13)	0.0049 (12)	0.0035 (14)

Br1—C4	1.904 (2)	C2—H2	0.9300
S1—O2	1.4228 (19)	C3—C4	1.380 (4)
S1—O1	1.4369 (19)	C3—H3	0.9300
S1—N1	1.635 (2)	C4—C5	1.374 (3)
S1—C8	1.755 (3)	C5—C6	1.400 (3)
N1—C1	1.415 (3)	C5—H5	0.9300
N1—C9	1.464 (3)	C6—C7	1.479 (3)
N2—C7	1.280 (3)	C7—C8	1.515 (3)
N2—N3	1.388 (3)	C8—H8A	0.9700
N3—H32	0.85 (4)	C8—H8B	0.9700
N3—H31	0.90 (4)	C9—H9A	0.9600
C1—C2	1.397 (4)	C9—H9B	0.9600
C1—C6	1.404 (3)	C9—H9C	0.9600
C2—C3	1.369 (4)
O2—S1—O1	118.29 (11)	C5—C4—Br1	120.2 (2)
O2—S1—N1	108.09 (11)	C3—C4—Br1	118.40 (19)
O1—S1—N1	110.45 (11)	C4—C5—C6	120.6 (2)
O2—S1—C8	111.38 (11)	C4—C5—H5	119.7
O1—S1—C8	107.55 (12)	C6—C5—H5	119.7
N1—S1—C8	99.44 (11)	C5—C6—C1	118.1 (2)
C1—N1—C9	121.3 (2)	C5—C6—C7	120.0 (2)
C1—N1—S1	115.59 (16)	C1—C6—C7	121.9 (2)
C9—N1—S1	118.49 (17)	N2—C7—C6	118.9 (2)
C7—N2—N3	117.8 (2)	N2—C7—C8	120.9 (2)
N2—N3—H32	105 (2)	C6—C7—C8	120.1 (2)
N2—N3—H31	112 (2)	C7—C8—S1	111.17 (16)
H32—N3—H31	115 (3)	C7—C8—H8A	109.4
C2—C1—C6	119.7 (2)	S1—C8—H8A	109.4
C2—C1—N1	120.0 (2)	C7—C8—H8B	109.4
C6—C1—N1	120.2 (2)	S1—C8—H8B	109.4
C3—C2—C1	121.4 (2)	H8A—C8—H8B	108.0
C3—C2—H2	119.3	N1—C9—H9A	109.5
C1—C2—H2	119.3	N1—C9—H9B	109.5
C2—C3—C4	118.8 (2)	H9A—C9—H9B	109.5
C2—C3—H3	120.6	N1—C9—H9C	109.5
C4—C3—H3	120.6	H9A—C9—H9C	109.5
C5—C4—C3	121.4 (2)	H9B—C9—H9C	109.5
O2—S1—N1—C1	177.43 (17)	C4—C5—C6—C1	−0.3 (3)
O1—S1—N1—C1	−51.7 (2)	C4—C5—C6—C7	−178.8 (2)
C8—S1—N1—C1	61.13 (19)	C2—C1—C6—C5	1.4 (3)
O2—S1—N1—C9	−26.3 (2)	N1—C1—C6—C5	−177.3 (2)
O1—S1—N1—C9	104.5 (2)	C2—C1—C6—C7	179.8 (2)
C8—S1—N1—C9	−142.6 (2)	N1—C1—C6—C7	1.1 (3)
C9—N1—C1—C2	−13.4 (3)	N3—N2—C7—C6	179.0 (2)
S1—N1—C1—C2	142.1 (2)	N3—N2—C7—C8	−0.3 (4)
C9—N1—C1—C6	165.3 (2)	C5—C6—C7—N2	3.4 (3)
S1—N1—C1—C6	−39.2 (3)	C1—C6—C7—N2	−174.9 (2)
C6—C1—C2—C3	−1.4 (4)	C5—C6—C7—C8	−177.2 (2)
N1—C1—C2—C3	177.3 (2)	C1—C6—C7—C8	4.4 (3)
C1—C2—C3—C4	0.4 (4)	N2—C7—C8—S1	−155.8 (2)
C2—C3—C4—C5	0.6 (4)	C6—C7—C8—S1	24.9 (3)
C2—C3—C4—Br1	−178.47 (19)	O2—S1—C8—C7	−165.88 (17)
C3—C4—C5—C6	−0.7 (4)	O1—S1—C8—C7	63.0 (2)
Br1—C4—C5—C6	178.42 (17)	N1—S1—C8—C7	−52.11 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H32···N2i	0.85 (4)	2.47 (4)	3.198 (4)	144 (3)
N3—H31···O1ii	0.90 (4)	2.38 (4)	3.252 (4)	162 (3)
C3—H3···O1iii	0.93	2.45	3.323 (3)	156.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H32⋯N2i	0.85 (4)	2.47 (4)	3.198 (4)	144 (3)
N3—H31⋯O1ii	0.90 (4)	2.38 (4)	3.252 (4)	162 (3)
C3—H3⋯O1iii	0.93	2.45	3.323 (3)	156

Symmetry codes: (i) ; (ii) ; (iii) .